Conformationally restricted formyl methionyl tripeptide chemoattractants: a three-dimensional structure-activity study of analogs incorporating a C alpha,alpha-dialkylated glycine at position 2

The conformationally restricted CHO-L-Met-Xxx-L-Phe-OY (where Xxx = Aib, Ac3c, Ac5c, Ac6c, and Ac7c; Y = H, Me) tripeptides, analogs of the chemoattractant CHO-L-Met-L-Leu-L-Phe-OH, have been synthesized in solution by classical methods and fully characterized. Compounds were compared to determine the combined effect of backbone conformational preferences and side-chain bulkiness on the relation of three-dimensional structure to biological activity. Each peptide was tested for its ability to induce granule enzyme secretion from rabbit peritoneal polymorphonuclear leukocytes. In parallel, a conformational analysis on the CHO-blocked peptide and their tertbutyloxycarbonylated synthetic precursors was performed in the crystal state and in solution using X-ray diffraction, infrared absorption, and 1H nuclear magnetic resonance. The biological and conformational data are discussed in relation to the proposed model of the chemotactic peptide receptor of rabbit neutrophils.

Molecular model for localised modes in zincblende structures

A molecular model for substitutional defects in a zincblende lattice has been worked out. The infrared absorption due to A1 in InSb and Li in GaAs are interpreted on the basis of this model.

Raman spectrum of strontium titanate

The Raman spectrum of strontium titanate has been recorded using λ 4358 of mercury as exciter. The observed spectrum consists of 7 Raman lines, one of which is of low frequency, as expected from the recent theory of Cochran. 6 of these Raman lines have been interpreted as the first order spectrum arising from a small deviation of the cubic strontium titanate from its idealized symmetry. It has been shown that one normal mode of SrTiO3 neglected by J.T. Last, will be really active in infrared absorption in the region of 440 cm-1 and that it has to be taken into account in the interpretation of the infrared spectra of titanates. The four vibrational modes of the unit cell of SrTiO3 correspond to frequencies of 90, 335, 441 and 620 cm-1 observed in Raman effect. The large width of the Raman lines and the additional lines at 256 cm-1 and 726 cm-1 have been attributed to a splitting of the longitudinal and transverse optical modes. With the observed frequencies it has been found possible to account for in a satisfactory manner the specific heat of SrTiO3 in the range 54·84° K to 1800° K.

Structural characterization of gel-grown neodymium copper oxalate single crystals

Sparingly soluble neodymium copper oxalate (NCO) single crystals were grown by gel method, by the diffusion of a mixture of neodymium nitrate and cupric nitrate into the set gel containing oxalic acid. Tabular crystal, revealing well-defined dissolution figures has been recorded. X-ray diffraction studies of the powdered sample reveal that NCO is crystalline. Infrared absorption spectrum confirmed the formation of oxalato complex with water of crystallization, while energy dispersive X-ray analysis established the presence of neodymium dominant over copper in the sample. X-ray photoelectron spectroscopic studies established the presence of Nd and Cu in oxide states besides (C2O4)(2-) oxalate group. The intensities of Nd (3d(5/2)) and Cu (2p(3/2)) peaks measured in terms of maximum photoelectron count rates also revealed the presence of Nd in predominance. The inductively coupled plasma analysis supports the EDAX and XPS data by the estimation of neodymium percentage by weight to that of copper present in the NCO sample. On the basis of these findings, an empirical structure for NCO has been proposed. The implications are discussed.

Investigations on sodium tin phosphate and tin pyrophosphate glasses

Glasses of the alkali tin phosphate system have been investigated. The infrared absorption and fluorescence spectra of the glasses have been examined. It is found that tin is present in both + 2 and + 4 oxidation states. Also tin ions occupy four- or six-coordinated sites in the glass.

Interplay of spin and lattice degrees of freedom in the frustrated antiferromagnet CdCr2O4: High-field and temperature-induced anomalies of the elastic constants

Temperature and magnetic field studies of the elastic constants of the chromium spinel CdCr2O4 show pronounced anomalies related to strong spin-phonon coupling in this frustrated antiferromagnet. A detailed comparison of the longitudinal acoustic mode propagating along the 111] direction with a theory based on an exchange-striction mechanism leads to an estimate of the strength of the magnetoelastic interaction. The derived spin-phonon coupling constant is in good agreement with previous determinations based on infrared absorption. Further insight is gained from intermediate and high magnetic field experiments in the field regime of the magnetization plateau. The role of the antisymmetric Dzyaloshinskii-Moriya interaction is discussed.

Conformational Stability and Intramolecular Hydrogen Bonding in 1,2-Ethanediol and 1,4-Butanediol

The gas-phase infrared spectra of 1,2-ED and 1,4-BD have been, recorded at three different temperatures using a multipass gas cell of 6 m optical path length. DFT calculation has also been carried out using 6-311++G** and aug-cc-pVDZ basis sets to look for the existence of intramolecular hydrogen bonding, in them from the red shift and infrared absorption intensity enhancement of the bonded O-H band compared to that of the free O-H hand. Equilibrium population analysis With 10 conformers of 1,2-ED and 1,4-BD at experimental temperatures were-carried out for the reconstruction of the Observed vibrational spectra at that temperature,using standard statistical relationships. The most abundant conformer at experimental temperatures, was identified. In 1,2-ED a red shift of 45 cm(-1) in the intramolecularly interacting O-H stretching vibrational band position and no significant intensity enhancement compared to that of-the free O-H have been observed. On the contrary, in one of the hydrogen bonded conformers of 1,4-BD, a 124 cm(-1) red shift in the O-H stretching frequency and 8.5 times-intensity enhancement for the ``bonded'' O-H compared to that of the ``free'' O-H is seen. On the basis of this comparative study, we have concluded that strong intramolecular hydrogen bonding exists in 1,4-BD. But there appears, to be weak intramolecular hydrogen bonding in 1,2-ED at temperatures of 303, 313, and 323 Km the gas phase We have found that most stable hydrogen-bonded conformers of 1,4-BD are less populated than some of the non-hydrogen-bonded conformers. Even for the 1,4-BD, the relative population of the g'GG'Gt conformer, which has a strong intramolecular,hydrogen bond, is less than what is predicted. Perhaps the intramolecular hydrogen bond plays a less Significant role in the relative stability,of the various Conformers than what has been predicted from calculations and prevails in the literature.

Films de polietileno oxo-degradados mediante envejecimiento acelerado por radiación UV y calor

Resumen: Los materiales plásticos utilizados en la industria del embalaje y transporte de mercaderías familiares e industriales, presentan numerosas ventajas que los han puesto en su lugar durante los últimos 50 años. En la actualidad, son miles de millones de toneladas anuales de bolsas o embalajes de polietileno, las que diariamente se producen, se usan, se recuperan (en muy pequeña parte) y son finalmente dispuestas, quemadas o literalmente arrojadas al medio ambiente. La alta estabilidad química o la muy baja tasa de degradación, hace que estos residuos perduren en el medio - en la mayoría de los casos por más de 100 años- dependiendo las condiciones ambientales locales. Hace pocos años, se adaptaron conocimientos científicos a esta problemática, y de ello nacieron dos formas de atacar la eliminación del plástico como desecho (más allá del reciclado y uso racional): por un lado, la utilización de bioplásticos con propiedades biodegradables; y por otro, el agregado de aditivos pro-degradantes a plásticos convencionales. El presente trabajo, tiene por objeto tomar a esta última herramienta, sobre la cual se han comenzado a estudiar los mecanismos químicos por los cuales cumplen su función, evaluándolos en distintas condiciones aceleradas de laboratorio. De esta manera, se caracterizaron velocidades de degradación abiótica mediante envejecimientos acelerados con radiación ultravioleta y térmica, para films de polietileno aditivados con un compuesto oxodegradante comercial. Se estudiaron distintas concentraciones de aditivo en el polímero, en función del tiempo de envejecimiento. Las caracterizaciones incluyeron análisis mecánico, análisis térmico diferencial, espectroscopía de absorción infrarroja y de Absorción Atómica.

Optical properties of excited silicon and germanium at low temperatures

Part I of this thesis deals with 3 topics concerning the luminescence from bound multi-exciton complexes in Si. Part II presents a model for the decay of electron-hole droplets in pure and doped Ge.

Part I.

We present high resolution photoluminescence data for Si doped With Al, Ga, and In. We observe emission lines due to recombination of electron-hole pairs in bound excitons and satellite lines which have been interpreted in terms of complexes of several excitons bound to an impurity. The bound exciton luminescence in Si:Ga and Si:Al consists of three emission lines due to transitions from the ground state and two low lying excited states. In Si:Ga, we observe a second triplet of emission lines which precisely mirror the triplet due to the bound exciton. This second triplet is interpreted as due to decay of a two exciton complex into the bound exciton. The observation of the second complete triplet in Si:Ga conclusively demonstrates that more than one exciton will bind to an impurity. Similar results are found for Si:Al. The energy of the lines show that the second exciton is less tightly bound than the first in Si:Ga. Other lines are observed at lower energies. The assumption of ground state to ground-state transitions for the lower energy lines is shown to produce a complicated dependence of binding energy of the last exciton on the number of excitons in a complex. No line attributable to the decay of a two exciton complex is observed in Si:In.

We present measurements of the bound exciton lifetimes for the four common acceptors in Si and for the first two bound multi-exciton complexes in Si:Ga and Si:Al. These results are shown to be in agreement with a calculation by Osbourn and Smith of Auger transition rates for acceptor bound excitons in Si. Kinetics determine the relative populations of complexes of various sizes and work functions, at temperatures which do not allow them to thermalize with respect to one another. It is shown that kinetic limitations may make it impossible to form two-exciton complexes in Si:In from a gas of free excitons.

We present direct thermodynamic measurements of the work functions of bound multi-exciton complexes in Al, B, P and Li doped Si. We find that in general the work functions are smaller than previously believed. These data remove one obstacle to the bound multi-exciton complex picture which has been the need to explain the very large apparent work functions for the larger complexes obtained by assuming that some of the observed lines are ground-state to ground-state transitions. None of the measured work functions exceed that of the electron-hole liquid.

Part II.

A new model for the decay of electron-hole-droplets in Ge is presented. The model is based on the existence of a cloud of droplets within the crystal and incorporates exciton flow among the drops in the cloud and the diffusion of excitons away from the cloud. It is able to fit the experimental luminescence decays for pure Ge at different temperatures and pump powers while retaining physically reasonable parameters for the drops. It predicts the shrinkage of the cloud at higher temperatures which has been verified by spatially and temporally resolved infrared absorption experiments. The model also accounts for the nearly exponential decay of electron-hole-droplets in lightly doped Ge at higher temperatures.

LiNbO3∶Fe∶Rh晶体近红外非挥发全息记录

采用双中心记录方案在双掺杂LiNbO3∶Fe∶Rh晶体中实现了近红外非挥发全息记录,研究了LiNbO3∶Fe∶Rh晶体在633 nm,752 nm,799 nm波长下的全息记录性能。结果表明,在使用近红外记录光时,其记录灵敏度随敏化光强的变化趋势与双中心短波长记录时的不同。通过和LiNbO3∶Fe∶Mn等传统双掺杂铌酸锂晶体的近红外波段记录效果对比,发现同时掺杂Fe和Rh可增强晶体对近红外光的吸收,获得更高的浅中心Fe光生伏特系数,从而能够在LiNbO3∶Fe∶Rh晶体中实现近红外波段的光折变全息记录。

Photoinduced effects in amorphous Ge-Se films

With light illumination from an Ar ion laser, the photoinduced changes in vacuum evaporated amorphous GeSe2 films; were investigated with the X-ray diffraction (XRD), infrared absorption (IR), scanning electron microscope (SEM), transmitting electron microscope (TEM) and transmittance spectra analysis. It was observed that the optical transmittance edges of films shifted to shorter wavelength according to annealing and light illumination and the shift in well-annealed films could be recovered by annealing at 200 degrees C for 1 h in Ar air. The magnitude of shift increased with the increase of the intensity of illumination light and the illumination time. By sides, photoinduced crystallization was also observed in the exposed regions of GeSe2 films and more of it was observed with stronger intensity of illumination light.

TCNQ脂类衍生物及其铜复合物的合成与红外光谱研究

首次合成了7，7，8，8-四氰基对苯醌二甲烷的脂类衍生物：TCNQ（C2H4COOR）2（R=CH3，C2H5，C3H7）及其铜电子转移复合物。通过元素分析确定这些化合物的组成，对这些化合成物在4000～400cm^-1范围内的主要红外光谱吸收峰进行了归属，并讨论了取代基对TCNQ类衍生物红外光谱的影响及其规律。

TeO2对氟铝酸盐玻璃性质和结构的影响

以10MgF2—20CaF2—10SrF2—10BaF2—15YF3—35AlF3氟铝酸盐玻璃为基玻璃引入不同含量的TeO2得到了新的氟碲铝酸盐玻璃．用差热分析方法研究了TeO2对氟铝酸盐玻璃性能的影响，通过拉曼光谱和红外吸收谱来研究玻璃的结构变化．差热分析表明TeO2的增加使玻璃开始析晶温度瓦升高，融化温度％降低，成玻璃能力增加．玻璃结构分析表明氟碲铝酸盐玻璃的结构中存在[FnAl-O—AlFn]、[TeO3]、[TeO2F]和[TeOF2]等多面体，这些多面体由F^-和O^2-离子连接．这种新的氟碲铝

Structural investigation on TeO2-BiCl3 glassy system

Glass systems of composition xBiCl(3)-(1-x)TeO2 (x=0.2, 0.4, 0.5 and 0.6, respectively) have been investigated by means of DSC, infrared absorption spectroscopy and Raman spectroscopy in order to obtain information about the transformation of structure, thermal and optical properties in the formation of the glass network. The results confirm that the addition of BiCl3 network former increases the glass forming ability and the optical transmission range. And also from Raman results a structural evolution was observed where the number of structural units described as [TeO3] trigonal pyramids, [TeO3+1] polyhedra and ionic behavior bonds (NBO) increases at the expense of the [TeO4] trigonal bipyramids. Bi3+ ions exist in network structure as [BiO6] or [BiCl6] octahedral coordination. As upconversion luminescence glass host, this glassy system is desired for optical properties but the thermal stability will still be improved. (c) 2005 Elsevier B.V. All rights reserved.

铝酸镧单晶体中Ce^3＋的能级结构和荧光特性

采用提拉法成功生长了纯LaAlO3和掺铈的LaAlO3单晶体，测试了它们的远红外吸收谱，紫外吸收谱，荧光谱，根据吸收光谱确定了晶体中Ce^3+的能级结构，利用这一能级结构模型较好地解释了Ce：LaAlO3晶体的荧光光谱。